JP2017071100A - Black plated resin component and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a black plated resin component which can secure corrosion resistance by a corrosion resistant film, and make the corrosion resistant film prevent a jet-black black plated layer from having yellowness.SOLUTION: There is provided a black plated resin component which has: a resin base material; a base plating layer that is formed on the resin base material and contains a copper plated layer and a nickel plated layer in this order; a black chromium plated layer that is formed on the nickel plated layer, is formed from trivalent chromium and has a film thickness of 0.15 μm or more; and a corrosion resistant film that is formed on the black chromium plated layer, is formed from chromium phosphate or molybdenum phosphate, and has a film thickness of 7 nm or more, where as for brightness of the black chromium plated layer seen through the corrosion resistant film, in an L*a*b* color system, L* is 54 or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a black plating resin part used for a decorative part for a vehicle, a casing part for an electric product, and the like.

  In fields such as decorative parts for vehicles and casings for electrical appliances, there is a growing need for a deep blackish black appearance from the viewpoint of design and the like. Jet black tone black can be obtained with a black plating layer such as cobalt chrome plating (Patent Document 1), but this black plating layer lacks corrosion resistance.

  Therefore, conventionally, a chromate film has been formed on the black plating layer by chromate treatment using hexavalent chromium for improving the corrosion resistance. Although corrosion resistance performance can be ensured by this, as a contradiction, the hexavalent chromium component contained in the chromate film is strongly yellow, and the blackish black color of the black plating layer becomes yellowish when viewed through the chromate film. was there.

JP 2014-1000080 A

  Accordingly, an object of the present invention is to provide a black plated resin part that can ensure corrosion resistance by the corrosion resistant film and that the jet black tone black plating layer is not yellowish by the corrosion resistant film.

  When the black chrome plating layer is bright black with L * in the L * a * b * color system exceeding 54, the black plating layer formed of the hexavalent chromium component of the chromate film The yellow tint is inconspicuous, but in the case of a dark (deep) black with L * of 54 or less, the yellow tint has been found to be conspicuous, and as a result of intensive studies, the present invention has been achieved. .

(1) The black plated resin component of the present invention is formed on a resin base material, a base plating layer including a copper plating layer and a nickel plating layer formed on the resin base material in this order, and the nickel plating layer. A corrosion-resistant coating comprising a black chromium plating layer made of trivalent chromium having a thickness of 0.15 μm or more and a corrosion-resistant film made of chromium phosphate or molybdenum phosphate made of chromium phosphate or molybdenum phosphate formed on the black chromium plating layer. The lightness of the black chromium plating layer seen through the film is characterized in that L * is 54 or less in the L * a * b * color system.

(2) The method for producing a black-plated resin component of the present invention includes forming a base plating layer including a copper plating layer and a nickel plating layer in this order on a resin substrate, and performing electrolytic plating in a trivalent chromium plating bath. A black chromium plating layer made of trivalent chromium with a thickness of 0.15 μm or more is formed on the nickel plating layer by chemical conversion, and chromium phosphate or molybdenum phosphate is formed on the black chromium plating layer by chemical conversion treatment using a chemical conversion treatment solution. A corrosion-resistant film having a thickness of 7 nm or more is formed.

[Action]
When the black chrome plating layer has a film thickness of 0.15 μm or more, color variation in film thickness can be minimized. In addition, when the black chrome plating layer is deep black of L * 54 or less, if the corrosion-resistant film thereon has a yellow color, yellowing becomes noticeable. However, in the present invention, since the corrosion-resistant film is made of chromium phosphate (trivalent chromium) or molybdenum phosphate that does not substantially develop a yellow color, the black chromium plating layer is not yellowish. When this corrosion-resistant film has a thickness of 7 nm or more, corrosion resistance can be ensured.

  ADVANTAGE OF THE INVENTION According to this invention, corrosion resistance performance can be ensured with a corrosion-resistant film | membrane, and the black plating resin component by which a jet black tone black plating layer does not turn yellow with a corrosion-resistant film | membrane can be provided.

It is sectional drawing of the black plating resin component of Example 1, 2 which actualized this invention.

1. Resin base resin The resin base resin may be thermoplastic or thermosetting, and is not particularly limited, but acrylonitrile-butadiene-styrene copolymer (ABS) resin, polycarbonate (PC) resin, PC / ABS resin, acrylic resin Examples thereof include styrene resin, polyamide resin, polycarbonate resin, polypropylene resin, vinyl chloride resin, and polyurethane resin. ABS resin and PC / ABS resin are preferable from the viewpoints of strength, durability and the like.
On the resin base material, a conductive layer necessary for electrolytic plating of the next base plating layer is formed. Although it does not specifically limit as a conductive layer, An electroless nickel plating layer can be illustrated.

2. Underplating layer The underplating layer includes a copper plating layer and a nickel plating layer in this order. The copper plating layer is highly ductile and follows the resin substrate well. The nickel plating layer is a black chrome plating layer. Maintains aesthetics and is electrochemically anticorrosive. The specific configuration of the nickel plating layer is not particularly limited, and may be one layer or a plurality of layers.

3. Black chrome plating layer The film thickness of the black chrome plating layer is more preferably 0.15 μm or more. Although the upper limit of the film thickness of a black chromium plating layer is not specifically limited, 1 micrometer is preferable. When the thickness exceeds 1 μm, the internal stress of the film increases and the film is easily broken.
The color of the black chrome plating layer seen through the corrosion-resistant film is L * a * b * color system, L * is 44 to 50, a * is 1.5 to -1.5, and b * is 8 to -8. It is preferable to be within the range. If L * is less than 44, the blackness is too strong and the metal feeling is lost, and if a * and b * are outside this range, the respective colors (red, green, yellow, blue) become strong.
It is preferable that the black chrome plating layer contains Fe because corrosion resistance is improved.
Examples of the trivalent chromium compound used in the trivalent chromium plating bath is not particularly limited, chromium sulfate _{(Cr 2 (SO 4) 3} ), chrome alum _{(CrK (SO 4) 2)} , chromium nitrate (Cr (NO _{3 3} ), chromium chloride (CrCl ₃ ), chromium acetate (Cr (CH ₃ COO) ₃ ) and the like.

4). Corrosion-resistant film Although the upper limit of the film thickness of a corrosion-resistant film is not specifically limited, 20 nm is preferable. When this film thickness is thick, it becomes slightly white.
The chemical conversion treatment solution is an aqueous solution containing phosphoric acid and an additive metal. When a chromium phosphate film is formed, the additive metal is trivalent chromium, and when the molybdenum phosphate film is formed, the additive metal is molybdenum.
The chemical conversion treatment can also be performed by electroless treatment.

5. Applications of black-plated resin parts For decorative parts for vehicles (radiator grills, fenders, garnishes, wheel caps, back panels, air spoilers, emblems, etc.), electrical products (mobile phones, smart phones, personal digital assistants, game machines, etc.) Case components can be exemplified. In particular, decorative parts for vehicles that are exposed to wind and rain are required to have high corrosion resistance, and therefore have high effectiveness when the present invention is applied.

  The black plated resin parts of Examples 1 and 2 shown in FIG. 1 and Table 1 were prepared, and the black plated resin parts of Comparative Examples 1 to 4 shown in Table 1 were also prepared for comparison, and color measurement and corrosion resistance tests were performed. It was.

[Example 1]
As shown in FIG. 1 and Table 1, the black plated resin component of Example 1 is made of an ABS resin resin substrate (with an electroless nickel plating layer as a conductive layer) and copper formed on the resin substrate. A film thickness of 0.2 μm made of a base plating layer including a plating layer, a semi-bright nickel plating layer, a bright nickel plating layer, and a microporous nickel plating layer in this order, and trivalent chromium formed on the nickel plating layer And a corrosion-resistant film having a thickness of about 10 nm comprising a chromium phosphate film formed on the black chromium plating layer. The color of the black chrome plating layer seen through the corrosion-resistant film is L * a * b * color system, L * is 52.46, a * is 0.67, and b * is 4.38. It is. There is no yellowing of the black chrome plating layer due to the corrosion-resistant film.

  In order to produce the black plated resin part of Example 1, first, the resin base material surface was pretreated so as to impart conductivity to the resin base material surface. In the pre-treatment, the ABS resin substrate is immersed in chromic acid and etched, and the surface after the etching treatment is activated by applying a Pd—Sn metal complex to form an electroless nickel plating layer as a conductive layer. did.

  Then, the base plating process was performed to the resin base material which provided electroconductivity by pre-processing. In the base plating process, a copper plating layer, a semi-bright nickel plating layer, a bright nickel plating layer, and a microporous-nickel plating layer are stacked in this order by electrolytic plating by immersing the resin substrate in various metal plating baths. The process was performed.

Next, the black chrome plating process was performed to the resin substrate which carried out the base plating process. In the black chrome plating treatment, the resin substrate subjected to the base plating treatment is immersed in a trivalent chromium plating bath, the bath temperature is 40 ° C., the pH value is 3.2, the cathode current density is 10 A / dm ² , the anode current density is 10 A / dm ² , The electroplating was carried out under conditions of a film forming rate of 0.07 μm / min and a plating time of 3 minutes, whereby a black chromium plating layer having a thickness of 0.2 μm was formed on the microporous nickel plating layer. The trivalent chromium plating bath used is an aqueous solution containing the following components (the trivalent chromium compound is a basic chromium sulfate contained in trichrome azide), and pH is further adjusted using 35% hydrochloric acid. The value was adjusted to 3.2.
Wako Pure Chemical Industries Boric acid 63g / L
Atotech Trichrome Additive 400g / L
Atotech Trichrome Stabilizer 100ml / L
Atotech Trichrome Regulator 3ml / L
Atotech Trichrome Collector 2ml / L
Atotech Trichrome Graphite Makeup 100ml / L

  Next, a chemical conversion treatment was performed on the black chrome-plated resin substrate. The chemical conversion treatment is carried out by electroless treatment under the conditions that the resin substrate that has been subjected to black chrome plating treatment is subjected to chemical conversion treatment liquid and the liquid temperature is 25 ° C., pH value is 1.3, and chemical conversion treatment time is 60 seconds. A chromium phosphate film having a thickness of about 10 nm was formed on the plating layer. The chemical conversion treatment solution used was an aqueous solution (phosphate chromate treatment solution) containing 89% phosphoric acid solution at 12.5 ml / L and 10 g / L of chromium sulfate as a trivalent chromium compound.

[Example 2]
As shown in FIG. 1 and Table 1, the black plated resin part of Example 2 has a resin base material, a base plating layer, and a black chromium plating layer in common with Example 1, and a corrosion-resistant film having a thickness of about 10 nm. This is different from Example 1 only in that it is made of a molybdenum film. The color of the black chrome plating layer seen through the corrosion-resistant film is L * a * b * color system, L * is 51.83, a * is 0.68, b * is 4.64, and jet black black It is. There is no yellowing of the black chrome plating layer due to the corrosion-resistant film.

  In order to manufacture the black plating resin component of Example 1, first, as in Example 1, pretreatment of the resin base material, base plating treatment, and black chrome plating treatment were performed.

Next, a chemical conversion treatment was performed on the black chrome-plated resin substrate. The chemical conversion treatment is performed by immersing the black chrome-plated resin substrate in a chemical conversion treatment solution under conditions of a liquid temperature of 30 ° C., a pH value of 12, a current density of 0.5 A / dm ² , and a chemical conversion treatment time of 180 seconds. A molybdenum phosphate film having a thickness of about 10 nm was formed on the black chromium plating layer. The chemical conversion treatment solution used was an aqueous solution containing 110 g / L of potassium sulfate, 13 ml / L of 89% phosphoric acid solution, and 5 g / L of sodium molybdate dihydrate.

[Comparative Example 1]
As shown in Table 1, the black plated resin part of Comparative Example 1 is different from Example 1 only in that the resin base material, the base plating layer, and the black chrome plating layer are common to Example 1 and are not provided with a corrosion-resistant film. To do. The color of the black chrome plating layer is L * a * b * color system, L * is 52.01, a * is 0.67, and b * is 4.36, which is black in black. Of course, the black chrome plating layer is not yellowish.

  In order to manufacture the black plating resin component of Comparative Example 1, as in Example 1, pretreatment of the resin base material, base plating treatment, and black chrome plating treatment were performed.

[Comparative Example 2]
As shown in Table 1, the black plated resin part of Comparative Example 2 has a resin base material, a base plating layer, and a black chromium plating layer in common with Example 1, and a hexavalent chromium chromate film having a corrosion resistance film of about 10 nm in thickness. This is different from the first embodiment only in this point. The color of the black chrome plating layer seen through the corrosion-resistant film is L * a * b * color system, L * is 51.11, a * is 0.97, and b * is 7.2. It is. There is a yellow tint of the black chrome plating layer by the corrosion-resistant film.

  In order to manufacture the black plating resin component of Comparative Example 2, first, as in Example 1, pretreatment of the resin base material, base plating treatment, and black chrome plating treatment were performed.

Next, a chemical conversion treatment was performed on the black chrome-plated resin substrate. The chemical conversion treatment is performed by immersing the black chrome-plated resin substrate in a chemical conversion treatment liquid, under conditions of a liquid temperature of 40 ° C., a pH value of 3.0, a current density of 0.5 A / dm ² , and a chemical conversion treatment time of 180 seconds. As a result, a hexavalent chromium chromate film having a thickness of about 10 nm was formed on the black chromium plating layer. The chemical conversion treatment solution used was a 25 wt% chromic anhydride aqueous solution.

[Comparative Example 3]
As shown in Table 1, in the black plating resin part of Comparative Example 3, the resin base material and the base plating layer are the same as in Example 1, and the black plating layer is composed of a cobalt chromium plating layer and a cobalt oxide layer thereon. This is different from Example 1 in that it does not have a corrosion-resistant film. The color of the black plating layer is L * a * b * color system, L * is 51.65, a * is 0.26, and b * is 1.85, which is a jet black tone. Naturally, there is no yellowing of the black plating layer.

  In order to manufacture the black-plated resin part of Comparative Example 3, as in Example 1, pretreatment of the resin base material and base plating treatment were performed.

Next, the black cobalt chromium plating process was performed to the resin substrate which carried out the base plating process. In the black plating treatment, the resin substrate subjected to the base plating treatment is immersed in a cobalt chromium plating bath, the bath temperature is 50 ° C., the pH value is 3.5, the cathode current density is 10 A / dm ² , the anode current density is 5 A / dm ² , and the film is formed. This is performed by electrolytic plating under conditions of a speed of 0.1 μm / min and a plating time of 15 minutes, whereby a black cobalt chromium plating layer made of a cobalt chromium alloy having a thickness of 1.5 μm on the microporous nickel plating layer. Formed. The cobalt chrome plating bath used is a sulfate solution with a metal content concentration of Cr ³⁺ of 30 g / L and a metal content concentration of Co ²⁺ of 3 g / L. In addition, a conductive salt, pH buffer, surface conditioning Containing an agent and the like.

  Subsequently, a black cobalt chrome-plated resin substrate was taken out, and the surface was subjected to acid dipping treatment to form a cobalt oxide layer. The acid immersion treatment was performed by immersing the resin substrate in a treatment tank filled with an organic acid having a pH value of 1.5 and maintaining the treatment temperature at 50 ° C. for 10 minutes. By this acid immersion treatment, oxidation of the surface layer portion of the black cobalt chrome plating layer progressed to form a cobalt oxide layer, and the blackness of the surface layer portion increased, resulting in a jet black tone.

[Comparative Example 4]
As shown in Table 1, the black plating resin part of Comparative Example 4 has the same resin base material and undercoat plating layer as in Example 1, the black plating layer in common with Comparative Example 3, and the corrosion-resistant coating film. This is different from Example 1 in that it is made of a hexavalent chromium chromate film having a thickness of about 10 nm. The color of the black chrome plating layer is L * a * b * color system, L * is 48.25, a * is 0.76, and b * is 3.95, which is black in black. There is a yellow tint of the black chrome plating layer by the corrosion-resistant film.

  In order to manufacture the black plating resin component of Comparative Example 4, the pretreatment of the resin base material and the base plating treatment were performed in the same manner as in Example 1, and the black cobalt chromium plating treatment and the acid were conducted in the same manner as in Comparative Example 3. Immersion treatment was performed.

Next, a chemical conversion treatment was performed on the black-plated resin substrate. The chemical conversion treatment is performed by immersing the black-plated resin substrate in a chemical conversion treatment solution under conditions of a liquid temperature of 40 ° C., a pH value of 3.0, a current density of 0.5 A / dm ² , and a chemical conversion treatment time of 5 minutes. As a result, a hexavalent chromium chromate film having a thickness of about 10 nm was formed on the black plating layer. The chemical conversion treatment solution used was a 25 wt% chromic anhydride aqueous solution.

The samples of the produced black plated resin parts of Examples 1 and 2 and Comparative Examples 1 to 4 were subjected to color measurement and corrosion resistance test by CASS test.
<Color measurement>
The color of the black plating layer was measured with a spectrocolorimeter (CM-700d manufactured by Konica Minolta). The measurement conditions were measurement mode SCI, observation condition 10 ° field of view, observation light source D65, measurement diameter / illumination diameter = φ3 / φ6. Each value in the measured L * a * b * color system is as described above (Table 1).

<Corrosion resistance test>
A CASS test (JIS H 8502) was conducted under the following conditions.
Test solution: sodium chloride 40 g / L, cupric chloride 0.205 g / L, pH 3.0
Saturator temperature 63 ℃
Test tank temperature 50 ℃
Spray amount 1.5ml / 80cm ² / h
Compressed air pressure 0.98 MPa
Sample installation angle 30 °
Test time 50h
After the CASS test was completed, the sample was taken out, washed with water, wiped off moisture, and the rating number was determined by comparing the corrosion state of the surface with the rating number table (Table 1). Rating number 8 or higher was accepted.

  In addition, this invention is not limited to the said Example, In the range which does not deviate from the meaning of invention, it can change suitably and can be actualized.

Claims (10)

  A film thickness of 0.15 μm comprising a resin base material, a base plating layer including a copper plating layer and a nickel plating layer formed in this order on the resin base material, and trivalent chromium formed on the nickel plating layer The lightness of the black chrome plating layer provided with the above-mentioned black chrome plating layer and a corrosion-resistant film having a thickness of 7 nm or more made of chromium phosphate or molybdenum phosphate formed on the black chrome plating layer, as seen through the corrosion-resistant film, A black plated resin part characterized in that L * is 54 or less in the L * a * b * color system.   The color of the black chrome plating layer seen through the corrosion-resistant film is L * a * b * color system, L * is 44 to 50, a * is 1.5 to -1.5, and b * is 8 to -8. The black-plated resin part according to claim 1, which is within a range.   The black plated resin part according to claim 1, which is a decorative part for a vehicle.   A base plating layer including a copper plating layer and a nickel plating layer in this order is formed on a resin substrate, and a film thickness of trivalent chromium is formed on the nickel plating layer by electrolytic plating in a trivalent chromium plating bath. A black chromium plating layer having a thickness of 15 μm or more is formed, and a corrosion-resistant film having a thickness of 7 nm or more made of chromium phosphate or molybdenum phosphate is formed on the black chromium plating layer by chemical conversion treatment using a chemical conversion treatment solution. The manufacturing method of the black plating resin component to be.   The manufacturing method of the black plating resin component of Claim 4 with which a chemical conversion liquid contains phosphoric acid and an addition metal.   6. The method for producing a black plated resin part according to claim 5, wherein the additive metal is trivalent chromium.   The method for producing a black plated resin part according to claim 5, wherein the additive metal is molybdenum.   The method for producing a black-plated resin part according to any one of claims 4 to 7, wherein the chemical conversion treatment is an electroless treatment.   The method for producing a black-plated resin part according to any one of claims 4 to 8, wherein the brightness of the black chromium plating layer viewed through the corrosion-resistant film is L * a * b * color system and L * is 54 or less. .   The color of the black chrome plating layer seen through the corrosion-resistant film is L * a * b * color system, L * is 44 to 50, a * is 1.5 to -1.5, and b * is 8 to -8. It is in the range. The manufacturing method of the black plating resin component as described in any one of Claims 4-9.

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